CN101654425B - L-proline trifluoromethanesulfonic acid ammonium salt and application thereof - Google Patents
L-proline trifluoromethanesulfonic acid ammonium salt and application thereof Download PDFInfo
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- CN101654425B CN101654425B CN2009101525097A CN200910152509A CN101654425B CN 101654425 B CN101654425 B CN 101654425B CN 2009101525097 A CN2009101525097 A CN 2009101525097A CN 200910152509 A CN200910152509 A CN 200910152509A CN 101654425 B CN101654425 B CN 101654425B
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Abstract
The invention relates to an L-proline trifluoromethanesulfonic acid ammonium salt and an application thereof. The L-proline trifluoromethanesulfonic acid ammonium salt is prepared from trifluoromethanesulfonic acid and L-proline. The L-proline trifluoromethanesulfonic acid ammonium salt can be applied to catalyze a condensation reaction of three components of aldehyde, amide and phenol, wherein the condensation reaction of the three components of the aldehyde, the amide and the phenol is completely carried out in an organic solvent under the action of a trifluoromethanesulfonic acid ammonium salt by using the phenol and the aldehyde and the amine as raw materials, and then reaction liquid is separated and purified to obtain a corresponding multicomponent condensation product. The invention develops a novel trifluoromethanesulfonic acid ammonium salt, thereby promoting the application of acid organic catalysts of a new generation in multicomponent reactions and meanwhile promoting the further development of the multicomponent reactions.
Description
(1) technical field
The present invention relates to a kind of novel trifluoromethanesulfacid acid ammonium salt--the L-proline trifluoromethanesulfacid acid ammonium salt and in aldehyde, acid amides and phenol three component condensation reactions as Application of Catalyst.
(2) background technology
Trifluoromethanesulfacid acid ammonium salt is a kind of novel acid organic catalyst.Compare with the traditional Lewis acid (as aluminum chloride) and the rare earth metal Lewis acid catalyst of newly-developed, that this organic catalyst has is stable to water, only need catalytic amount, heavy metal free to pollute, can be recycled and advantage such as low price, thereby be a kind of green catalyst efficiently, have favorable actual application prospect.After the carboxylic acid that time trifluoromethanesulfonic acid hexichol ammonium salt (DPAT) is used for the catalysis equivalent from scientific research the first in the group of Tanabe in 2000 leader and the esterification of alcohol, the application of trifluoromethanesulfacid acid ammonium salt in organic synthesis obtained great development, has been used to numerous acid catalyzed reactions.
In recent years, organic synthesis technology has had development at full speed, and new theory, new reaction, novel agent constantly occur, and product yield is further improved, and synthesis step is simpler, and lock out operation is also simplified greatly.Because multi-component reaction occupies very big advantage at aspects such as the simplification of Atom economy, environmental friendliness, step, resources effective utilizations,, be " blowout formula " development in recent years more near the ideal building-up reactions.The traditional Lewis acid and the rare earth metal Lewis acid catalyst of newly-developed are all applied to various multi-component reactions widely, for example Mannich reaction, Biginelli reaction, Diels-Alder reaction, Hantzsch reaction, Ugi reaction etc.Can obtain using more widely in this field as novel acid organic catalyst trifluoromethanesulfacid acid ammonium salt.
The amino phenol that is obtained by aldehyde, acid amides and phenol three component condensation reactions is a kind of at the pharmaceutical intermediate of widespread use pharmaceutically, traditional synthetic method mainly is to utilize an acidic catalyst catalysis synthetic, iodine for example, iron(ic) chloride, tosic acid etc., shortcomings such as but it exists the reaction times longer, and catalyzer is difficult for reclaiming, and while substrate suitability is not extensive.
(3) summary of the invention
The primary technical problem that the present invention will solve provides a kind of novel trifluoromethanesulfacid acid ammonium salt--L-proline trifluoromethanesulfacid acid ammonium salt.
L-proline trifluoromethanesulfacid acid ammonium salt of the present invention is to be prepared by trifluoromethanesulfonic acid and L-proline(Pro).
Described L-proline trifluoromethanesulfacid acid ammonium salt can prepare by the following method: under condition of ice bath, trifluoromethanesulfonic acid slowly is added drop-wise in the reaction solvent that is dissolved with the L-proline(Pro), control reaction temperature is between-50～30 ℃, reacted 10～90 minutes, and obtained the L-proline trifluoromethanesulfacid acid ammonium salt through conventional aftertreatment.
Described reaction solvent can be selected from the mixing of following a kind of or any several arbitrary proportions: the halogenated alkane of C1～C5, the fatty ester of C1～C8, ketone, ethers, alcohols, benzene,toluene,xylene, chlorobenzene, hexanaphthene, water; The ketone of the preferred C3～C5 of described ketone, the ether of the preferred C3～C5 of described ethers, the alcohol of the preferred C1～C5 of described alcohols; The mixing of the preferred following a kind of or any several arbitrary proportions of reaction solvent of the present invention: the alcohol of C1～C5, toluene, hexanaphthene, water.
Second technical problem that the present invention will solve is that the L-proline trifluoromethanesulfacid acid ammonium salt is applied to provide the preparation method of a kind of technology polycomponent condensation product simple, with low cost in aldehyde, acid amides and the phenol three component condensation reactions as catalyzer.
Aldehyde, acid amides and phenol three component condensation reactions can be used following general formula:
Wherein component (I) is the L-proline trifluoromethanesulfacid acid ammonium salt.
Wherein component (II) is a phenol, can be phenol, naphthols etc.
Wherein component (III) is an aldehyde, can be alkanoic or aromatic aldehyde or heterocyclic aldehydes.
Wherein component (IV) is an acid amides, can be fatty amide or aromatic amides.
Product (V) is the polycomponent condensation product that obtains.
Aldehyde of the present invention, acid amides and phenol three component condensation reactions specifically can be adopted following technical scheme: with phenol and aldehyde and acid amides is raw material, fully reaction under reflux temperature in organic solvent under the effect of L-proline trifluoromethanesulfacid acid ammonium salt, the reaction solution separation and purification promptly gets corresponding polycomponent condensation product.
The preferred described phenol of the present invention is one of following: naphthols, phenol.
The preferred described aldehyde of the present invention is one of following: alkanoic, aromatic aldehyde, heterocyclic aldehydes.
Alkanoic of the present invention is the aldehyde compound that aldehyde radical is connected with aliphatic group, and described aliphatic group can be the fat chain alkylene, also can be alicyclic hydrocarbon radical; The chain alkylene of the preferred C1～C10 of described fat chain alkylene is as acetaldehyde, isovaleric aldehyde etc.; The cyclic hydrocarbon radical of the preferred C3～C7 of described alicyclic hydrocarbon radical is as cyclohexyl aldehyde etc.
Aromatic aldehyde of the present invention is the aldehyde compound that aldehyde radical is connected with aryl, and described aryl comprises phenyl, substituted-phenyl, fragrant heterocycle and phenyl etc.; Wherein the substituting group of substituted-phenyl can be one or more, and substituting group can be alkoxyl group, alkyl, halogen, nitro, hydroxyl etc.; Wherein fragrant heterocycle and phenyl can be indoles, thionaphthene, cumarone etc.
Heterocyclic aldehydes of the present invention is the aldehyde compound that aldehyde radical is connected with heterocyclic group, as Furan Aldehydes, thiophene aldehyde etc.
The preferred described acid amides of the present invention is one of following: fatty amide, aromatic amides.
Fatty amide of the present invention is the amides that amide group is connected with aliphatic group, and the chain alkylene of the preferred C1～C10 of described aliphatic group is as ethanamide, butyramide etc.
Aromatic amides of the present invention is the amides that amide group is connected with aryl, and described aryl comprises phenyl, substituted-phenyl, fragrant heterocycle and phenyl etc.; Wherein the substituting group of substituted-phenyl can be one or a plurality of, and substituting group can be alkoxyl group, alkyl, halogen, nitro, hydroxyl etc.; Wherein fragrant heterocycle and phenyl can be indoles, thionaphthene, cumarone etc.
It is 1: 0.8～1.2: 0.9～1.3 that the present invention recommends the described molar ratio that contains phenol, aldehyde, acid amides.
The molar ratio of preferred described L-proline trifluoromethanesulfacid acid ammonium salt of the present invention and phenol is 0.02～1.0: 1, preferred 0.05～0.4: 1.
The organic solvent that aldehyde of the present invention, acid amides and phenol three component condensation reactions are suitable for can be selected from following halogenated alkane, the fatty ester of C1～C8, ketone, ethers, alcohols, benzene,toluene,xylene, chlorobenzene, hexanaphthene a kind of or several combinations: C1～C5 arbitrarily; The ketone of the preferred C3～C5 of described ketone, the ether of the preferred C3～C5 of described ethers, the alcohol of the preferred C1～C5 of described alcohols; One of described organic solvent is preferred following: methylene dichloride, trichloromethane, 1,1-ethylene dichloride, 1,2-ethylene dichloride, ethyl acetate, toluene.The consumption of organic solvent is recommended as 10～25ml/g in the quality of phenol.
Follow the tracks of reaction with TCL in the reaction process, after reaction finished, available routine operation carried out separation and purification, specifically can adopt following method: gained reaction solution water and ethyl acetate extraction, get organic layer, and concentrated, organic solvent recrystallization promptly gets corresponding condensation product.
The recrystallization solvent that recrystallization is suitable in aldehyde of the present invention, acid amides and the phenol three component condensation reaction aftertreatments can be selected from the mixture of following a kind of or any several arbitrary proportions: the halogenated alkane of C1～C5, the fatty ester of C1～C8, ketone, ethers, alcohols, benzene,toluene,xylene, chlorobenzene, hexanaphthene; The ketone of the preferred C3～C5 of described ketone, the ether of the preferred C3～C5 of described ethers, the alcohol of the preferred C1～C5 of described alcohols; The mixture of the preferred following a kind of or any several arbitrary proportions of described recrystallization solvent: methylene dichloride, trichloromethane, 1,1-ethylene dichloride, 1,2-ethylene dichloride, ethyl acetate, acetone, methyl alcohol, ethanol, hexanaphthene.The volumetric usage of recrystallization solvent is 2～20 times of phenol quality preferably.
The present invention compared with prior art, its beneficial effect is embodied in:
That the novel trifluoromethanesulfacid acid ammonium salt that the present invention makes--L-proline trifluoromethanesulfacid acid ammonium salt has is stable to water, only need catalytic amount, heavy metal free to pollute, can be recycled and advantage such as low price, use it for aldehyde, acid amides and naphthols three component condensation reactions, has the advantage that technology is simple, cost is low, and yield reaches as high as 95%, has enriched the application of organic ammonium salt catalyzer of new generation in multi-component reaction.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
Under condition of ice bath, with trifluoromethanesulfonic acid (0.750g, 5.0mmol) slowly be added drop-wise to L-proline(Pro) (0.580g, 5.0mmol) the aqueous solution (10mL) in, control reaction temperature is between-5 ℃～5 ℃, reacted 30 minutes, and concentrated after the petroleum ether and obtain L-proline trifluoromethanesulfacid acid ammonium salt 1.23g, yield 93%.
Embodiment 2
Under condition of ice bath, with trifluoromethanesulfonic acid (0.750g, 5.0mmol) slowly be added drop-wise to L-proline(Pro) (0.580g, 5.0mmol) toluene solution (10mL) in, control reaction temperature is between-5 ℃～5 ℃, reacted 30 minutes, and concentrated after the petroleum ether and obtain L-proline trifluoromethanesulfacid acid ammonium salt 1.14g, yield 86%.
Embodiment 3
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), phenyl aldehyde (0.106g, 1.0mmol), (0.133g is 1.1mmol) with L-proline trifluoromethanesulfacid acid ammonium salt (0.026g for benzamide, 0.1mmol), reaction under trichloromethane (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, concentrated, and re-crystallizing in ethyl acetate promptly gets corresponding condensation product, yield 95%.
White?solid；mp?242-243℃；
1H?NMR(500MHz，DMSO-d
6)：δ＝7.20-7.32(m，8H，Ar-H)，7.47-7.50(m，3H，Ar-H)，7.54-7.57(m，1H，Ar-H)，7.79-7.87(m，4H，Ar-H)，8.08(d，J＝8.5Hz，1H，Ar-H)，9.03(d，J＝8.5Hz，1H，NH)，10.33(s，1H，OH)；
13C?NMR(100MHz，DMSO-d
6)：δ＝49.7，118.8，119.1，123.2，126.9，127.0，127.2，127.6，128.7，128.8，129.0，129.1，129.9，129.1，129.9，131.9，132.8，134.8，142.4，153.6，166.2；IR(KBr)：3422，3147，1629，1538，1400，1347，822，751，582cm
-1；MS(ESI)：m/z＝352[M
-].
Embodiment 4
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), phenyl aldehyde (0.117g, 1.1mmol), (0.145g is 1.2mmol) with L-proline trifluoromethanesulfacid acid ammonium salt (0.026g for benzamide, 0.1mmol), reaction under trichloromethane (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, concentrated, and re-crystallizing in ethyl acetate promptly gets corresponding condensation product, yield 89%.
Embodiment 5
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), 4-chloro-benzaldehyde (0.141g, 1.1mmol), benzamide (0.133g, 1.1mmol) and the L-proline trifluoromethanesulfacid acid ammonium salt (0.026g, 0.1mmol), reaction under methylene dichloride (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, concentrated, and ethyl alcohol recrystallization promptly gets corresponding condensation product, yield 93%.
Embodiment 6
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), m-nitrobenzaldehyde (0.151g, 1.0mmol), benzamide (0.133g, 1.1mmol) and the L-proline trifluoromethanesulfacid acid ammonium salt (0.026g, 0.1mmol), reaction under methylene dichloride (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, concentrated, and ethyl acetate, ethyl alcohol recrystallization promptly get corresponding condensation product, yield 92%.
Embodiment 7
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), isovaleric aldehyde (0.095g, 1.1mmol), (0.133g is 1.1mmol) with L-proline trifluoromethanesulfacid acid ammonium salt (0.026g for benzamide, 0.1mmol), 1,2-ethylene dichloride (2mL) reflux conditions is reaction down, and TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, and concentrated, ethyl alcohol recrystallization promptly gets corresponding condensation product, yield 86%.
White?solid；mp?252-253℃；
1H?NMR(400MHz，DMSO-d
6)：δ＝0.94-0.99(m，6H，CH
3)，1.57-1.71(m，2H，CH
2)，2.16-2.23(m，1H，CH)，6.06-6.12(m，1H，CH)，7.17(d，J＝1.8Hz，1H，Ar-H)，7.19-7.31(m，1H，Ar-H)，7.44-7.54(m，4H，Ar-H)，7.69(d，J＝4.0Hz，1H，Ar-H)，7.78-7.82(m，3H，Ar-H)，8.19(s，1H，NH)，8.58(s，1H，Ar-H)，10.09(s，1H，OH)；
13C?NMR(100MHz，DMSO-d
6)：δ＝21.9，23.2，25.0，43.0，45.1，118.7，120.2，122.4，126.3，127.0，128.4，128.6，131.1，131.9，134.7，152.9，165.4；IR(KBr)：3421，3177，2955，1638，1536，1437，1342，813，750，704cm
-1；MS(ESI)：m/z＝332[M
-]；HRMS-EI：m/z[M]calcd?forC
22H
23NO
2：333.1726；found：333.1745.
Embodiment 8
Adding 1-naphthols in the 25mL two-mouth bottle (0.144g, 1.0mmol), phenyl aldehyde (0.106g, 1.0mmol), (0.133g is 1.1mmol) with L-proline trifluoromethanesulfacid acid ammonium salt (0.026g for benzamide, 0.1mmol), reaction under trichloromethane (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, concentrated, and acetone recrystallization promptly gets corresponding condensation product, yield 71%.
Embodiment 9
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), 4-chloro-benzaldehyde (0.140g, 1.0mmol), (0.060g is 1.1mmol) with L-proline trifluoromethanesulfacid acid ammonium salt (0.026g for ethanamide, 0.1mmol), reaction under methylene dichloride (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, and concentrated re-crystallizing in ethyl acetate promptly gets corresponding condensation product, yield 94%.
Embodiment 10
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), NSC 43794 (0.136g, 1.0mmol), ethanamide (0.060g, 1.1mmol) and the L-proline trifluoromethanesulfacid acid ammonium salt (0.260g, 1mmol), reaction under methylene dichloride (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, and concentrated re-crystallizing in ethyl acetate promptly gets corresponding condensation product, yield 95%.
Embodiment 11
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), 4-chloro-benzaldehyde (0.140g, 1.0mmol), ethanamide (0.060g, 1.1mmol) and the L-proline trifluoromethanesulfacid acid ammonium salt (0.005g, 0.02mmol), reaction under methylene dichloride (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, and concentrated re-crystallizing in ethyl acetate promptly gets corresponding condensation product, yield 46%.
Embodiment 12
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), isovaleric aldehyde (0.086g, 1.0mmol), ethanamide (0.060g, 1.1mmol) and the L-proline trifluoromethanesulfacid acid ammonium salt (0.026g, 0.1mmol), 1,2-ethylene dichloride (2mL) reflux conditions is reaction down, and TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, and concentrated recrystallizing methanol promptly gets corresponding condensation product, yield 85%.
Embodiment 13
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), phenylacrolein (0.132g, 1.0mmol), ethanamide (0.060g, 1.1mmol) and the L-proline trifluoromethanesulfacid acid ammonium salt (0.026g, 0.1mmol), 1,1-ethylene dichloride (2mL) reflux conditions is reaction down, and TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, and concentrated ethyl alcohol recrystallization promptly gets corresponding condensation product, yield 81%.
Embodiment 14
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), 4-chloro-benzaldehyde (0.140g, 1.0mmol), (0.095g is 1.1mmol) with L-proline trifluoromethanesulfacid acid ammonium salt (0.026g for butyramide, 0.1mmol), reaction under methylene dichloride (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, and concentrated re-crystallizing in ethyl acetate promptly gets corresponding condensation product, yield 68%.
Embodiment 15
In the 25mL two-mouth bottle, add beta naphthal (0.144g, 1.0mmol), Furan Aldehydes (0.106g, 1.1mmol), ethanamide (0.060g, 1.1mmol) and the L-proline trifluoromethanesulfacid acid ammonium salt (0.026g, 0.1mmol), 1,1-ethylene dichloride (2mL) reflux conditions is reaction down, and TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, and concentrated ethyl alcohol recrystallization promptly gets corresponding condensation product, yield 79%.
Embodiment 16
Adding 1-naphthols in the 25mL two-mouth bottle (0.144g, 1.0mmol), phenyl aldehyde (0.117g, 1.1mmol), (0.060g is 1.1mmol) with L-proline trifluoromethanesulfacid acid ammonium salt (0.026g for ethanamide, 0.1mmol), reaction under trichloromethane (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, concentrated, and re-crystallizing in ethyl acetate promptly gets corresponding condensation product, yield 81%.
Embodiment 17
In the 25mL two-mouth bottle, add phenol (0.094g, 1.0mmol), phenyl aldehyde (0.106g, 1.0mmol), (0.133g is 1.1mmol) with L-proline trifluoromethanesulfacid acid ammonium salt (0.026g for benzamide, 0.1mmol), reaction under trichloromethane (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, concentrated, and the methylene dichloride recrystallization promptly gets corresponding condensation product, yield 78%.
Embodiment 18
In the 25mL two-mouth bottle, add to biphenol (0.110g, 1.0mmol), phenyl aldehyde (0.106g, 1.0mmol), (0.133g is 1.1mmol) with L-proline trifluoromethanesulfacid acid ammonium salt (0.026g for benzamide, 0.1mmol), reaction under trichloromethane (2mL) reflux conditions, TCL follows the tracks of reaction.After reaction finished, water and ethyl acetate extraction were got organic layer, concentrated, and the hexanaphthene recrystallization promptly gets corresponding condensation product, yield 58%.
Claims (5)
1.L-proline trifluoromethanesulfacid acid ammonium salt in aldehyde, acid amides and phenol three component condensation reactions as Application of Catalyst;
It is one of following that described phenol is selected from: phenol, naphthols;
It is one of following that described aldehyde is selected from: alkanoic, aromatic aldehyde, heterocyclic aldehydes; Described alkanoic is the aldehyde compound that the cyclic hydrocarbon radical of the chain alkylene of C1～C10 or C3～C7 is connected with aldehyde radical; Described aromatic aldehyde is the aldehyde compound that phenyl, substituted-phenyl or fragrant heterocycle and phenyl are connected with aldehyde radical; The substituting group of described substituted-phenyl is one or more, and described substituting group is alkoxyl group, alkyl, halogen, nitro or hydroxyl; Described fragrant heterocycle and phenyl are indoles, thionaphthene or cumarone;
It is one of following that described acid amides is selected from: fatty amide, aromatic amides; Described fatty amide is the amides that the chain alkylene of C1～C10 is connected with amide group; Described aromatic amides is the amides that phenyl, substituted-phenyl or fragrant heterocycle and phenyl are connected with amide group; The substituting group of described substituted-phenyl is one or a plurality of, and described substituting group is alkoxyl group, alkyl, halogen, nitro or hydroxyl; Described fragrant heterocycle and phenyl are indoles, thionaphthene or cumarone.
2. application as claimed in claim 1, it is characterized in that described aldehyde, acid amides and phenol three component condensation reactions are: with phenol and aldehyde and acid amides is raw material, fully react in reflux temperature in organic solvent under the effect of L-proline trifluoromethanesulfacid acid ammonium salt, the reaction solution separation and purification promptly gets corresponding polycomponent condensation product.
3. application as claimed in claim 2 is characterized in that described organic solvent is selected from following halogenated alkane, the fatty ester of C1～C8, the ketone of C3～C5, the ether of C3～C5, the alcohol of C1～C5, benzene,toluene,xylene, chlorobenzene, hexanaphthene a kind of or several combinations: C1～C5 arbitrarily.
4. application as claimed in claim 2 is characterized in that the described molar ratio that contains phenol, aldehyde, acid amides is 1: 0.8～1.2: 0.9～1.3; The molar ratio of described L-proline trifluoromethanesulfacid acid ammonium salt and phenol is 0.02～1.0: 1.
5. as the described application of one of claim 1～4, it is characterized in that described heterocyclic aldehydes is Furan Aldehydes or thiophene aldehyde.
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| CN105859695B (en) * | 2016-05-20 | 2019-02-26 | 苏州大学 | The synthetic method of 2- aryl -3- (4- hydroxyl -2H- pyran-2-one -3- base) indole derivatives |
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| Title |
|---|
| Gholam Hossein Mahdavinia, et al..Silica supported perchloric acid (HClO4-SiO2): A mild, reusable and highly efficient heterogeneous catalyst for the synthesis of amidoalkyl naphthols.《Chinese Chemical Letters》.2008,第19卷1171-1174. * |
| GholamHosseinMahdavinia et al..Silica supported perchloric acid (HClO4-SiO2): A mild |
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